Total synthesis of macrocyclic glycosides, clemochinenosides A and B, and berchemolide, by fluorous mixture synthesis

Tetrahedron Letters

Volumn 50, Issue 45, 2009, Pages 6143-6149

  Kojima, Masaru ^a   Nakamura, Yutaka ^a   Ito, Shun ^a   Takeuchi, Seiji ^a  

^a NIIGATA UNIVERSITY OF PHARMACY AND APPLIED LIFE SCIENCES   (Japan)

Author keywords

Benzylidene group; Fluorous; Macrocyclic glycoside; Mixture synthesis

Indexed keywords

4 O (4 O F 13 BENZYL BETA DEXTRO GLUCOPYRANOSYL)SYRINGIC ACID; 4 O (4 O F 17 GLUCOPYRANOSYL)VANILLIC ACID; BERCHEMOLIDE; CLEMOCHINENOSIDE A; CLEMOCHINENOSIDE B; FLUORINE DERIVATIVE; GLYCOSIDE; SYRINGIC ACID; UNCLASSIFIED DRUG; VANILLIC ACID;

ARTICLE; CHEMICAL STRUCTURE; COLUMN CHROMATOGRAPHY; CYCLIZATION; HIGH PERFORMANCE LIQUID CHROMATOGRAPHY; METHODOLOGY; OPTICS; SYNTHESIS;

EID: 70349432418     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2009.08.068     Document Type: Article

References (34)

1. Sakurai N., Kobayashi M., Shigihara A., and Inoue T. Chem. Pharm. Bull. 40 (1992) 851
2. Yan L., Yang S., Zou Z., Luo X., and Xu L. Heterocycles 68 (2006) 1917
3. Song C.Q., and Xu R.S. Chin. Chem. Lett. 3 (1992) 119
4. Song C.Q., and Xu R.S. Chin. Chem. Lett. 4 (1993) 505
5. Shi S.-P., Jiang D., Dong C.-X., and Tu P.-F. Biochem. Syst. Ecol. 35 (2007) 57
6. Su D.-M., Wang Y.-H., Yu S.-S., Yu D.-Q., Hu Y.-C., Tang W.-Z., Liu G.-T., and Wang W.-J. Chem. Biodivers. 4 (2007) 2852
7. Wang Y., Mao J., and Cai M. Synth. Commun. 29 (1999) 2093
8. Luo Z., Zhang Q., Oderaotoshi Y., and Curran D.P. Science 291 (2001) 1766
9. Curran D.P., and Furukawa T. Org. Lett. 4 (2002) 2233
10. Zhang W., Luo Z., Chen C.H.-T., and Curran D.P. J. Am. Chem. Soc. 124 (2002) 10443
11. Zhang Q., Lu H., Richard C., and Curran D.P. J. Am. Chem. Soc. 126 (2004) 36
12. Curran D.P., Moura-Letts G., and Pohlman M. Angew. Chem., Int. Ed. 45 (2006) 2423
13. Fukui Y., Brückner A.M., Shin Y., Balachandran R., Day B.W., and Curran D.P. Org. Lett. 8 (2006) 301
14. Yang F., and Curran D.P. J. Am. Chem. Soc. 128 (2006) 14200
15. Jung W.-T., Guyenne S., Riesco-Fagundo C., Mancuso J., Nakamura S., and Curran D.P. Angew. Chem., Int. Ed. 47 (2008) 1130
16. Tojino M., and Mizuno M. Tetrahedron Lett. 49 (2008) 5920
17. Kojima M., Nakamura Y., and Takeuchi S. Tetrahedron Lett. 48 (2007) 4431
18. For reviews on FSPE, see:. Zhang W., and Curran D.P. Tetrahedron 62 (2006) 11837
19. Curran D.P. In: Gladysz J.A., Curran D.P., and Horváth I.T. (Eds). The Handbook of Fluorous Chemistry (2004), Wiley-VCH, Weinheim 101-127
20. Curran D.P. Synlett (2001) 1488
21. 10c].
22. ® column. When the fluorous compounds were sparingly soluble in MeOH, EtOAc or acetone was used to quickly elute the fluorous compounds from the column.
23. 3CN compared to that of 1.
24. 2, 0 °C, (y. 59%): Mukaiyama, T.; Usui, M.; Saigo, K. Chem. Lett. 1976, 5, 49.
25. ® silica gel (3 g) column and eluted with 80% aq MeOH (100 ml); the column was subsequently eluted with EtOAc (200 ml) to give a fraction containing Mixture-1 (94.5 mg).
26. 2O to 100:0 over a 10-min period. Compounds 11, 12, and 13 were eluted individually at 10.2, 13.3, and 16.7 min.
27. f values were large enough to separate the components by fluorous silica gel column chromatography depending upon their fluorine atom content. Comparatively, on a standard silica gel TLC, the top two spots were very close and the second spot overlapped with the tail of the top spot. Therefore, it was predicted that the three components would be difficult to separate by standard silica gel column chromatography without the fluorous tags. In addition, it is impossible to predict the structures of the components, even if separation was successful.
28. From 94.5 mg Mixture-1, homodimer 11 (18.5 mg), heterodimer 12 (47.8 mg), and homodimer 13 (14.4 mg) were obtained from 60%, 70%, and 100% aq THF fractions, respectively.
29. + 2107.4645, found: 2107.4657.
30. After purification of the crude products by FSPE, 4-(3-perfluoroalkyl)propyl toluenes were recovered from the MeOH fraction. (a) 4-(3-Perfluorohexyl)propyl toluene was obtained in 49% yield. (b) A mixture of 4-(3-perfluorohexyl)propyl toluene and 4-(3-perfluorooctyl)propyl toluene was obtained in 64% yield. (c) 4-(3-Perfluorooctyl)propyl toluene was obtained in 65% yield. Conversion of 4-(3-perfluoroalkyl)propyl toluenes into the corresponding 4-(3-perfluoroalkyl)propyl benzaldehydes for reuse is now in progress.
31. + 707.1799, found: 707.1793.
32. + 677.1694, found: 677.1695.
33. + 647.1588, found: 647.1612.
34. It was not possible to measure the optical rotation of the natural products. No samples of natural clemochinenosides A and B were available (Personal communication by Professor P.-F. Tu and Dr. S.-P. Shi).